Composition of matter and



, be characteristic str ct r pyrone in which a'methyl group is substituted on 35 Ptenled May 3, 1938 t STTES PATE GOMPOSKTIQN UFMATTER. ANDllIIETHUD F MAKING THE SAME Walter J. Koenig, Philadelphia, Pa., assignor to Sloane-Elation Corporation, Philadelphia, Pat, a coration of Delaware No Drawing. Application ember 22, 193d,

Serial No. 755,963

19 oi. (oi. act-2) This invention relates to a novel composition rical by the presence of an additional C-atom of matter to a novel method of making the same with a double bonded O-atom attached thereto. and to a novel method of drying oils and ole- I have found that the most desirable results are aginous compositions. More particularly the inattained when thissymmetrical structure is pres- 5 vention relates to an oleaginous composition for ent as in the case of maleic anhydrlde and 5 coating, plastics and the like especially adapted duinone.

for use in the manufacturing of floor covering Furthermore, I have found that the double materials, etc., and to resinous products derived bond of the characteristic structure should be in from said oleaginous compositions and to novel a position where it is free to break and combine methods by which the oleaginous compositions with the oil to form a new ring. If this results are reacted to form resinous products, and parin the formation of a double ring or a condensed ticularly to the method of drying such oleaginous nucleus compound re u t products Will 1 compositions by resin-forming reactions. sessed ofespecially desirable properties. If sub- This application is a continuation in part of my Stltution groups other than those indicated by the prior co-pending application Serial No. 646,148 bonds represented in the characteristic formula tiled September 7, 1932, entitled Composition of given above are present at the double bonded matter and method of making the same, now C-atoms they are likely to interfere with the con- Patent NO. 2,058,596. In my said prior applicad motion react on. tion I have disclosed the methods of drying oils Thus I have found that with phthalic a yby a resin-forming condensation and a number dride, although this characteristic structure is 20 of compositions suitable for drying by such meth- P One d u e bonded C- t is Common ods. With similar objects in view to those set to both rings o the p c anhydride Struciorth in my said prior application I have now dlsur therefore, has an additional Substitucovered that by combining the oil with a, resintionbeyond that indicated by the characteristic w forming compound adapted to condense thereo a ve V pp y for this "5 with so as to form a closed. chain by the union the Phthalic flnhydride preferentially oi the two molecules, especially desirable results denses with .the oil and at the double bonded may be obtained and the products will be ex- O-atoms. I have not yet been able to establish tremely tough and pliant. whether under favorable conditions the reaction to I have discovered furthermore that if the comcan be made to take place at the double bond to pound is a ring compound having a re ti e link.- the benzene ring, but I have established that this age at which it is adapted to combine with the mp und iv s h h y d i a and at a y molecule of the oil to form a closed ring strucdens o p o w the ture, and especially if it is a compound with the Another p d of this y fi y 0 one of the double bonded C-atoms. g Other compounds which exhibit this multiple substitution of a double bonded C-atom ,in the thatthe advantages of my invention will be most characteristic structure are citric anhydride,

to fully attained. citraconic anhydride, itaconicanhydrlde, and 40 In my said co-pending application I have dlspyrocinchon'ic anhydride. Substances of this closed the drying of oils with production of type, however, can be used satisfactorily and aptough, pliant resinous products by condensation parently form condensation products according with and alpha keto tetrahydro naphthato the present invention perhaps due to a moleculit lene. Research upon the condensation reaction lar rearrangement which is known frequently to involved indicates that the reaction occurs by the occur with compounds of this type. Citric acid destruction of one double bond, or, in other and the other acids corresponding to the anhywords, changing one double bond to a single bond drides mentioned and aconitic acid may also in the formation of a complex molecule, and it be used as raw materials since these are readily no further appears that the presence of the doubleconverted into the anhydrides underconditions bonded oxygen atom favors this condensation suitable for reaction with the oil. reaction. Fumaric acid and maleic acid may also be men- I have now found that other compounds having tioned as examples of the related compounds similar characteristic molecular structures react which are suitable for the purposes of my invenin a similar way to give especially desirable .contion although they do not include the charac- 55 densation products with the drying o ils. Most teristic structure directly. Both of these subdesirableiamong those which have been tried are stances may be converted into maleic anhydride maleic anhydride and quinone. In both of these under conditions suitable for reaction with the compounds it will be noted that the characterisoil. Maleic acid, furthermore, may be converted,

tic structure referred to above is made symmetin part at least, into coumallc acid in which the 60 'g I 2,110,073 I I I characteristic structure occurs in a lactone ring. e. g., sevenseconds blownChina-wood oil, by

As amply illustrated by' the above examples, the double bonded O-atom may be an oxygen of the anhydride structure. Apparently, however,

there is a steric hindrance if the oxygen is in a carboxylic acid group instead of in an anhydride group. Thus with fnaleic acid there is apparently no reaction with the oil until the temperature is reached at which the acid is converted into the anhydride after which a violent reaction occurs.

Referring .speciflcallyto maleic anhydride as one preferred example of my invention, I have found that the best results are obtained when the maleic acid or anhydride is present insubstan- 1 tially less than full molecular equivalent.

- I have found that the products having the most desirable properties are those which have the most complex molecular structure, and it is desirable therefore to choose condensations which so will give the largest and most complex molecules possible. I have found, for example, that if a condensation product. of the oil and maleie anhydride, especially one resulting from reacting molecular equivalents, is further condensed with 80 anithol, glycerol or terpineol, a more stable,

' tougher and especially a more alkali resistant film is produced. Apparently. these substances condense at the anhydride structure of the maleic molecule even after it has condensed with the oil '0 at its double bondedfC-atoms. This is more fully described and claimed in my application Serial .No. 758,864 filed herewith. l I

It will already have been appreciated by those skilled in the art that a feature ofprimary nu 80 portance of thepresent invention is that the re- It is of primary importance, moreover, that ac cording to the preseniinvention the reaction can be initiated en masse and then interrupted at a point short of complete drying. Thus the more 50 costly iinalstep of heating the finished article can be reduced to a very short treatment. with nearly all of the resin-forming condensation reagents this interruption can be so nearly complete that the partially reacted products can be 85 stored indefinitely at cool room temperatures.

The maleic anhydride reaction, however, does not stop at room temperatures, so that it is imp rtant to use the partially reacted materials promptly and not to make up too large stocks 60 of such materials in advance.

I have found that the reaction between them] I and the maleic anhydride will occur slowly and will tend gradually to solidify the oil even at atmospheric temperatures. If .the reaction is car- 5 ried too far at high temperature the oil may go solid immediately or before it can be used, but if the reaction is not carried too far at high temperature the drying will proceed slowly so that there will be adequate time to use the oils for 7 commercial purposes before they go solid. The

reaction with maleic anhydride proceedsslowly even at room temperature and rapidly at temperatures above 170 F. In practice I have found that it is most satisfactory to blend the maleic.

7g anhydride or maleic acid and China-wood oil, I

.The ingredients of the vehicle are refluxed at heating fairly rapidly to a temperatureof 'abouF 200 F. and then cooling almost immediately. Products thus made will keep for several weeks but will dry rapidly when heated, e. g., to a tem- I perature above 170 F..

As one example of an enamel made according to my present invention, I may blend 100 arts by weight or '1 seconds blown'China- 1 v wood oil 10 parts by weight of maleic anhydride Heat to 200 1 and allow to cool. A suilicient quantity of mineral spirits can then be added to obtain desired working properties.

The resulting vehicle may be ground with pigmerits in the usual way, e. g.,

- I Parts by weight Zinc oxide Lithopone 100 20 Barytes 100 a may be mixed in-100' parts of the vehicle just described and ground on a paint mill. The resulting composition is an excellent enamel, drying in 72 hours at 140 F. with a perfect gloss and an almost pure color-without discoloration from the vehicle. A

The vehicle may, of course, be used to form otherpaints or enamels, as will be obvious to those skilled in the art, or may be used alone as a varnish or protective coating, if cured at superatmospheric temperatures. I

It may also be 'used in plastic compositions as the adhesive binder. However. in this case, the M China-wood oil is preferably blown to a heavy consistency. Maleic anhydride is thenadded and the mixture heated with stirrlng at 275 F. to

proper consistency. The cement can be altered by the addition of resins, for example: I

- I Partsbyweight- Heavy blown China-wood oil 1050 "I" rosi 320 Kauri g .160 Maleic anhydride The. blown oil, 1" and Kauri gum are heated together while stirring at 250 to 275' I". Add'maleic' anhydride and continue heating at 275 1". and mixing until proper viscosity is hmy tained. After the maieic anhydride is added; the bodying effect is very rapid. Usually ten to fifteen minutes is sufficient.

Either of the above cements can be used in compositions. as follows:

Partsbyweight Peruvian ochre, or other pigments 15 'Wood flour 10 Ground cork 50 Gelled, or semi-solid vehicle '60 This vehicle may, for example, consist of 120 parts of blown China-wood oil, viscosity, nine seconds Gardner-Holt at 86 F. parts 25-gal. varnish (i. e. 25 gallons of China-wood oil m lbs. of phenol formaldehyde resin, such as bakelite I KB, 420, or Durez 525) /z Darts cyclohexanol 17% parts cyclohexanone dered by meansoi rolls, in the us ual way. I 75- For an inlaid llnoleunma similar procedure may be adopted preferably,' however, using a composition consisting of The reaction between the condensing reagent and the oil maytake place with very little oxidation, and the oil may be dried into excellent films in nitrogen containing only a trace of oxygen, (e. g., 0.2%) at super-atmospheric temperatures,

e. g., 140 F. to 220 F. A small amount of oxidation, however, does stimulate the reaction and improve the properties of the resulting products.

In this connection, also, I have found that, in general, for the resin-forming condensation drying slightly oxidized oils are preferred, e. g., a 'l" (Gardner-Holt) blown China-wood oil; apparently China-wood oils oxidized to the point at which the maximum peroxide is first reached are most reactive. At this point only one-third of the double bonds are oxidized, leaving two conjugate double bonds free for the condensation.

This is true in particular for the condensation with resin-forming compounds having the l 'VC=C&' structure according tothe present invention, i. e., slightly oxidized oils are'more advantageous.

- It will be noted that if two of the characterw istic chains referred to above are written together in a ring, viz.,

II ,Ii -cc= 0- the result is the formula of quinone. Thus there are two reactive linkages of these characteristic chains and apparently the oil molecules may. combine at both of these linkages so that the quinone may form a bridging molecule tying two molecules of the oil together, and thus forming a cpmplex molecular chain with the practical results that the oil is dried to form extremely high quality. hard and tough films.

Up to equi-molecular proportions an increase in the amount of quinone present improves the quality of the product. Beyond this point, however, further increases are not justified-by improved results. In considering reacting percentag es, however, it should be remembered that the quinone sublimes at the melting point.

When quinone is used as the condensing agent, the rate of drying of the film is slower than comparable films containing other condensing agents, but the resulting film is considerably .more alkali-resistant. This increased alkaline resistance is probably due to the formation of a more complex molecule. The preferred curing temperature is approximately 220 F. Below 180" F. the rate of drying is very slow and probably may not be considered a commercial success at the lower temperatures.

In order to avoid excessive sublimation of the quinone, I prefer to heat the mixture just enough to dissolve the quinorfe, or to carefully control the heatingpreferably with refluxing or pressure control. As one example of a vehicle made with quinone according to my invention, I may mix:

This vehicle may be used as a clear coating or may be solidified directly to form a resinous mass,

' tions of the condensing reagent should be limited.

bean .oil, blown or properly oxidized poppyseed oil, etc., castor oil heated under reduced presand esterified, blown or properly oxidized drying or it may be mixed with pigment or with fillers, etc., to form paint plastics, etc., e. g., as set forth above in connection with the maleic anhydride vehicles.

Other compounds may be used instead of maleic anhydride and quinone, as already mentioned. I have found that the most desirable of these compounds are the aromatic ketones having the characteristic structure, of which pyrone, coumarin and coumaranone may be given as further examples, and the closed ring anhydrides having said structure. And with all these' types I prefer those in which the unsaturated C-atoms are not attached to side chains or other rings.

In so far as these are heterocyclic compounds they fall specifically within the scope of my co- .pending application Serial No. 758,859, filed here with now Patent No. 2,058,597.

I have found that the presence of a small amount of reactive resin, such as phenol-formaldehyde and coumarone resins, is advantageously incorporated as a varnish or ground into the oil like a pigment improves greatly the properties of the resulting composition. As compared with the same composition, omitting the resin, a smoother film, more glossy and tougher, ordinarily results.

Various resins, both reactive and unreactive, may be, used in the composition as will be obvious to those skilled in the art of manufacturing paints and varnishes and plastics, etc.

It is to be understood that the proportions and the particular ingredients specified in the above examples are given only to illustrate the invention and the manner of practicing it by certain specific examples and that these proportions and ingredients can be varied within relatively wide limits without departing from the "scope of my invention. For example, it will be readily understood that the proportions of thinner, preferably mineral thinners, will depend primarily upon the consistency desired and this may be varied, as will be apparent to anyone skilled in.

the art.

As already stated, the proportions of the condensing reagents may be substantially varied. If it is desired to obtain the more flexible and tougher films characteristic of those formed by bonding molecules of the oils together with a condensing reagent capable of reacting at two parts of the same molecule with different molecules of the oil, it is important that the propor- Except for this an excess of the condensingreagent is not objectionable and will ordinarily be driven off as vapor during the heating or drying of the composition.

Other oils, in which I include treated and untreated drying oils, treated semi-drying oils and non-drying oils, that possess double bonds in conjugate arrangement, e. g., --C=CC=C--, or --C=C-C=C--C=C-, (such as, China-wood oil, fish oils, oiticica oil, blown or properly oxidized linseed oil, blown or properly oxidized soya sures to form conjugate double bond structure oil fatty acids, and the above treated and untreated oils, having the above double bond conjugate structure, blown with drying oil fattyacids or such oils to which blown or properly oxidized fatty acids have been added), fall within the scope of my invention.

I prefer to use blown or properly oxidized oils,

although the raw oils having above described conjugate double; bond arrangement will dry inaccordance with my invention.

With the characteristicfstructure referred to above, the reaction apparently primarily at a conjugate double bond such as is present in elaeostearic acid'ofChina-wood oil, or such as is present in fish oil, blown linseed and blown or dehydrated-caster oils. of all the comf =merci'ally available oils, China-wood oil-has been found to give the best results and other less advantageous oils may be improved by the addition of .fatty acids of China-wood oil, or by mixture of China-wood oil therewith. a

The temperatures specified in. the example have-been chosen, of course, with practical com mercial conditions in mind. Othertemperatures may be used. With quinone'higher are apparently necessary, but with other condensing reagents temperatures around 140 1?. may be preferable and temperatures as low even as 115 F. may be used; in some cases. Temperatures much above 200 F. may result in discoloration, and where they are not necessary, it is ordinarily desirable to maintain lower temperatures. However, I have used temperatures as high as 300 F. with very satisfactory results and in most cases even higher temperatures can be used.

In an example given above, drying. is pref-V erably conducted in an atmosphere of gases g ven 5 I off by the film, or in substantially pure, inert atmosphere.

Where a gelled vehicle is desired, the thinner may be partially or entirely omitted and the .heat treatment continued until the desired viscosity is obtained as will be readily understood by those skilled in the art. In this case also it may be desirable to body the oil to a somewhat heavier 4o consistency before the condensing reagent is added. a In the examples I have referred particularly to paints, enamels, varnishes, and plastics because the invention is of great practical importance in the field of 'fioor covering materials. It is to be understood, however, that my invention is of much wider application than the field of floor coverings and may be applied generally to all sorts of protective and decorative coatings and molded or machined resinous products, including besides paints, enamels and varnishes, such as would be used in floor covering, printing ink, lithographvarnishes, coatings for tin cans, etc., coating impregnatingand insulating varnishes, protectivev 'coatings for automobiles, machinery, furniture and other articles and plastics for electrical insulation, chemically resistant articles and household utensils, decorative objects, implements, handles, etc., to. mention only a few of the numerous applications of my invention.

It seems clear that-a condensation occurs. The extent of condensation depends on the condensing agents used, but regardless whether the condensation is partial or practically complete, the

reaction falls withinthe scope of this invention, since. my invention embraces rapid drying action at super-atmospheric temperatures in substan: tially non-oxidizing atmospheres as due to condensation.

In the case of partial condensation, i. e.',. where the amount of condensing agent is less than in stoichiometric relations, it is my theory that the presence of the particular type of condensation product of the .oil and condensing agents is reing a tougher film in the final product.

the

sponsiblei'or the rapid drying." The invention described herein cannot be construed in the samelig'ht as the action of driers, as the action proceeds unimpeded or rapidly, as the case may be,

in substantially non-oxidizing atmospheres at super-atmospheric temperatures with definite favorable results starting as low as F., which differentiates from polymerization and oxidation under similar conditions.

If more than one condensing' agent is used, it is not necessary'to add the several condensing agents as a mixture at th'e-startof the reaction.

The reaction may bestarted with a single condensing agent, andjafter the reaction has Progressed to any pointbefore becoming a solid mass, the reaction may-be retarded by merely cooling the mixture. Additional condensing agent may then be added, if desired, and the reaction accelerated again by merely raising the temperature. The'addition of more than one condensing agent tends to-create final products having more complexstructures, thereby creat- It is understood that the reaction may be retarded and accelerated any number of times before completion, and,v if desired, additional condensing agents may be added which enter the condensation reaction. If desired, an additional quantity of the original condensing agent or a mixture of the original and a diiferent type of condense ing agent may be added. It is, within the scope of this invention to include the addition of an additional quantity ofthe same condensing agent used at the start of the reaction and/or a different one at-any point in the reaction. The feature of accelerating and retarding the reaction at any desired point in the reaction is a very desirable point, and is accomplished by merely controlling the temperature. It is not necessary to add additional condensing agents to again accelerate the reaction after it has been retarded. although this may be done if so desired, as ex-, plained above. 4

In the above specification I have given examples and suggested certain modifications for the purpose of illustrating the invention without in any way attempting to exhaustively cover all of the various modifications and applications of my invention. Similarly, I have expressed certain theories which I'have developed in the course of my investigations and practical experience with this invention, which I believe may be helpful to those who subsequently apply and I extend the application of my invention. However, I have not as'yet tested these theories sumciently to set them up as certainly correct, and since the invention is in no way dependent upon the correctness ofv any'theories'which I have expressed,- it is to be'understood that the scope of my invention and of this application is not to be limited thereby. I have used the termcondensation" herein broadly to mean the union of two or more organic substances, with or without the elimination of componentelements.

What is claimed as new is:

1. The method of hardening drying oil which comprises condensing at super-atmospheric tem perature a mixture in which the condensation rea'ctantsconsist of 'oxidized drying oil having double bonds in conjugate arrangement and a cyclic organic compound having the characteri'stic structure I 2. The method as defined in claimsl, in which the surface of the oil is protected against too rapid oxidation during at least the final drying stage of said reaction.

3. The method as defined in claim 1, in which the condensation reaction occurs in the presence of synthetic resin.

4. The method as defined in claim 1, in which the characteristic structure is part of a closed ring anhydride of a polycarboxylic acid. 5. The method as defined in claim 1, in which the compound having the characteristic structure is maleic anhydride.

6. The method as defined, in claim 1, in which the condensed'mixture is cooled before hardening is complete, giving tothe mixture the useful shape which is desired of the hardened oil, and heating the shaped material at super-atmospheric temperature until hardening is complete.

4 7. The niethod as defined in claim 1, in which the hardening of the condensed mixture is carried on in an atmosphere substantially devoid of oxygen.

8. The method as defined in claim 1, in which the compound having the characteristic structure is present in amount about one-third the molecular equivalent of oil.

9. The method of hardening drying oil which comprises condensing at super-atmospheric temperature a mixture in which the condensation reactants consist of oxidized drying oil having double bonds in conjugate arrangement and a cyclic organic compound having the characteristic structure sac- 10. The method of hardening oxidized drying 011 whose molecular structure includes reactive double bonds in conjugate arrangement, which comprises condensing a mixture in which the condensation reactants consist of the drying oil and cyclic organic compounds having the characteristic structure -O=O&-

and being capable of condensation at the double bonded C atoms of the oil at super-atmospheric temperature.

11. The method of hardening drying oil into a tough, elastic film which comprises condensing a mixture in which the condensation reactants consist of drying oil having double bonds in coniugate arrangement and a cyclic organic compound having the characteristic structure 0 4.0-5- a, at super-atmospheric temperature until a desired viscosity is obtained. cooling the mixture, shaping temperature.

the mixture to the form desired of the hardened film, and finally heating the film at superatmospheric temperature until hardening is complate.

12. The method as described in claim 11, in

which the final step of heating the shaped film at super-atmospheric temperature until a desired viscosity is obtained, cooling the mixture, shaping the mixture to the form desired' of the hardened film, and finally heating the film at super-atmospheric temperature until hardening is complete.

15. The method as described in claim 14, in which the final step of heating the shaped film occurs in an atmosphere substantially devoid of oxygen.

16. A composition of matter comprising a coni densation mixture in which the. condensation reactants consist of oxidized drying oil having double bonds in conjugate arrangement and a cyclic organic compound having the characteristic structure o -C= O-5 17. A composition of matter comprising a condensation mixture in which the condensation reactants consist of oxidized drying oil having double bonds in conjugate arrangement and cyclic organic compounds having the characteristic structure 18. The method of drying an oil having double bonds in conjugate arrangement which comprises incorporating quinone with the oil and heating the mixture to a temperature above 200 F.,' whereby to condense the quinone with the oil.

19. The method of treating a drying oil to improve the drying properties, the step which comprises reacting a mixture which includes oxidized drying oil having double bonds in conjugate arrangement and quinone. said oil and quinone forming a condensation product at the double bonded C atoms 01' the oil at super-atmospheric wan-ma J. some. 

